EP1187876B1 - Injection moulding - Google Patents
Injection moulding Download PDFInfo
- Publication number
- EP1187876B1 EP1187876B1 EP00935303A EP00935303A EP1187876B1 EP 1187876 B1 EP1187876 B1 EP 1187876B1 EP 00935303 A EP00935303 A EP 00935303A EP 00935303 A EP00935303 A EP 00935303A EP 1187876 B1 EP1187876 B1 EP 1187876B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molecular weight
- weight
- hdpe
- fraction
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the invention relates to improvements in and relating to high density polyethylenes (HDPE) and in particular to the use of HDPE for injection moulding.
- HDPE high density polyethylenes
- HDPE is a polymer which is often used for the production by injection moulding of products used for packaging or containers.
- the HDPE materials conventionally used for these purposes are generally monomodal polyethylenes prepared using Ziegler-Natta catalysts.
- an injection moulded HDPE product is to be used to contain liquids where spillage would be environmentally undesirable, it is important that the moulded polymer is resistant to stress cracking. This may be measured by the environmental stress crack resistance (ESCR) test, a standardized ASTM test (e.g. ASTM D1693. Cond B).
- ESCR environmental stress crack resistance
- ASTM test e.g. ASTM D1693. Cond B
- HDPE injection moulding materials however have unsatisfactorily low ESCR values and thus are unsuitable for the production of injection moulded containers or other packaging materials for liquid chemical products, such as liquid chemicals, glues, paints, varnishes, solvent-based soaps etc.
- the polymers used for injection moulding are monomodal (ie. with a single peak in their molecular weight distributions). This is in order to avoid warpage.
- the invention thus provides the use in injection moulding, preferably in injection moulding of liquids containers, caps and closures, of a HDPE having a density of 950 to 980 kg/m 3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- the different components may both be ethylene copolymers and while one may be an ethylene homopolymer, the components cannot both be ethylene homopolymers.
- this is preferably the component with the lower weight average molecular weight (Mw), e.g. where Mw is 5000 to 100000 D, more preferably 20000 to 40000 D.
- the invention provides an injection moulded liquids container, preferably a container for liquids comprising an organic solvent, the walls whereof are formed from a HOPE having a density of 950 to 980 kg/m 3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- a HOPE having a density of 950 to 980 kg/m 3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- the invention provides an injection or extrusion moulded cap or closure, preferably a cap or closure for a container for beverages or liquids comprising an organic solvent, which cap or closure is formed from a HDPE having a density of 950 to 980 kg/m 3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- a HDPE having a density of 950 to 980 kg/m 3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- an HDPE for use in injection moulding, comprising at least two polyethylene components, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer.
- polyethylene By polyethylene is meant a polymer the majority by weight of which derives from ethylene monomer units. Minor comonomer contributions, e.g. up to 20% by weight more preferably up to 10% by weight, may derive from other copolymerizable monomers, generally C 3-20 , especially C 3-10 , comonomers, particularly singly or multiply ethylenically unsaturated comonomers; in particular C 3-10 ⁇ -olefins such as propene, but-1-ene, hex-1-ene, 4-methyl-pent-1-ene etc.
- ethylene copolymer is used herein to relate to a polyethylene deriving from ethylene and one or more such copolymerisable comonomers.
- the polyethylene may contain minor, e.g up to 10% by weight, preferably up to 5% by weight of other polymers, e.g. other polyolefins in particular polypropylenes, as well as additives such as colours, fillers, radiation stabilizers, antioxidants, etc., generally in amounts of up to 10% by weight, preferably up to 5% by weight.
- HOPE a polyethylene having a density of 950 to 980 kg/m 3 , preferably 950 to 975 kg/m 3 , especially 950 to 965 kg/m 3 and a crystallinity of 60 to 90%, preferably 70 to 90%.
- the HOPE according to the invention is a bimodal or multimodal polymer.
- bimodal or multimodal
- the polymer consists of at least two fractions (components), one of which has a relatively low molecular weight and a relatively high density and another of which has a relatively high molecular weight and a relatively low density.
- MWD molecular weight distribution
- the molecular weight distribution (MWD) of a polymer produced in a single polymerization stage using a single monomer mixture, a single polymerization catalyst and a single set of process conditions (ie. temperature, pressure etc.) will show a single maximum, the breadth of which will depend on catalyst choice, reactor choice, process conditions, etc, ie. such a polymer will be monomodal.
- a bimodal or multimodal polyethylene may be produced by blending two or more monomodal polyethylenes having differently centred maxima in their MWDs.
- the bimodal polyethylene may be produced by polymerization using conditions which create a bimodal or multimodal polymer product, e.g. using a catalyst system or mixture with two or more different catalytic sites, using two or more stage polymerisation process with different process conditions in the different stages (e.g. different temperatures, pressures, polymerisation media, hydrogen partial pressures, etc).
- Such a bimodal (or multimodal) HOPE may be produced relatively simply by a multistage ethylene polymerization, e.g. using a series of reactors, with comonomer addition in only the reactor(s) used for production of the higher/highest molecular weight component(s).
- Examples of bimodal PE production are given in EP-A-778289 and WO92/12182.
- ethylene homopolymer is produced by slurry polymerization involving use of recycled diluent, that diluent may contain small amounts of higher ⁇ -olefins as contaminants.
- ethylene homopolymer is meant herein a polymer containing at least 99.9% by weight of ethylene units.
- the homopolymerization catalysts may be at least partially active during the copolymerization reaction, any copolymer component making up less than 5% by weight of the total polymer shall not be considered to be the lowest molecular weight component in an HDPE according to the invention.
- the copolymer component(s) of the HDPE used according to the invention will generally contain at least 0.1% by weight, preferably at least 0.5% by weight of non-ethylene monomer units, e.g. 0.5 to 6% of such comonomer units.
- the polymerization reactions used to produce the HDPE of the invention may involve conventional ethylene homopolymerization or copolymerization reactions, e.g. gas-phase, slurry phase, liquid phase polymerizations, using conventional reactors, e.g. loop reactors, gas phase reactors, batch reactors etc. (see for example WO97/44371 and WO96/18662).
- the catalyst systems used may likewise be any conventional systems, e.g. chromium catalysts, Ziegler-Natta and metallocene or metallocene:aluminoxane catalysts, either homogeneous or more preferably heterogeneous catalysts, e.g.
- catalysts supported on inorganic or organic particulates in particular on magnesium halides or inorganic oxides such as silica, alumina or silica-alumina.
- inorganic or organic particulates in particular on magnesium halides or inorganic oxides such as silica, alumina or silica-alumina.
- supported Ziegler-Natta catalysts as the molecular weight can then conveniently be controlled using hydrogen.
- supported metallocene catalysts it is particularly straightforward to select desired molecular weights by appropriate selection of particular metallocenes.
- the metallocenes used will typically be group IVa to VIa metals (in particular Zr or Hf) complexed by optionally substituted cyclopentadienyl groups, e.g. groups carrying pendant or fused substituents optionally linked together by bridging groups. Suitable metallocenes and aluminoxane cocatalysts are widely described in the literature, e.g. the patent publications of Borealis, Ho
- the HOPE will be prepared using multistage polymerization using a single catalyst system or a plurality of catalyst systems, e.g. two or more metallocenes, one or more metallocenes and one or more Ziegler-Natta catalysts, two or more chromium catalysts, one or more chromium catalysts and one or more Ziegler-Natta catalysts, etc.
- a catalyst system as described in EP-A-688794.
- the properties of the HDPE used according to the invention preferably have the following values:
- MFR 2 of 50-1000 g/10 min, preferably 200-800 g/10 min, measured according to ISO 1133 at 190°C and under 2.16 kg load; weight average molecular weight of 5-50 kD, preferably 20-40 kD; preferably a homopolymer or a copolymer with density higher than 965 kg/m 3 , most preferably a homopolymer; comprises 10-90% by weight, preferably 40-60% by weight of the total polyethylene in the composition.
- Such HDPE may typically be prepared in a one or more stage polymerization, with the catalyst systems and process conditions in the individual stages being selected to produce polyethylene components of average molecular weights 5 to 100 kD and 150 to 400 kD in abundances of 1:9 to 9:1.
- containers produced in this fashion will have a volume of 100 mL to 100 L and caps and closures will typically have maximum dimensions of 10 to 600 mm.
- the injection moulding compositions of the invention have the further advantage of improved flow. This may be demonstrated using the 'spiral test'. In this procedure an Engel ES330/65 injection moulding apparatus is used with a spiral mould with a depth of 1, 2 or typically 3 mm. The composition flow rate at 230°C under 300, 500 and 700 bar follow up pressures is determined on the length of flow in the spiral. Typically a composition according to the invention with an MFR 2 value of about 4 g/10 min behaves like a conventional polyethylene with MFR 2 of about 8 g/10 min. See Table 1 below.
- the bimodal and multimodal HDPEs used according to the invention are particularly useful for extrusion coating, e.g. of paper or other substrates, producing coatings with low water vapor permeability and good coating draw down rates.
- Such use of the bimodal and multimodal HDPE's (especially ones with densities in excess of 935 kg/m 3 ) forms a further aspect of the invention.
- an HDPE comprising at least two polyethylene components, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer and having the following characteristics:
- an HDPE moulding composition comprising a particulate HOPE having the following characteristics:
- the invention provides an injection moulded article formed at least in part from an HDPE having the following characteristics:
- Example 1 and 2 Two bimodal polyethylene compositions (Samples 1 and 2) were prepared by mixing two of the three polyethylene components (A, B and C) listed in Table 1 into blends using an extruder (Werner & Pfleider ZSK 30W) operating at 193-194°C.
- Component Property Component A B C Mw(kD) 190 400 28 Mn (kD) 6 56 2.5 MWD 32 7 11 MFR 21 (g/10 min) 33 0.1 400 Density (kg/m 3 ) 955 927 974
- Sample 1 comprised 40% wt component C and 60% wt component A.
- Sample 2 comprised 60% wt component C and 40 wt% component B.
- the slurry was continuously removed from the loop reactor and introduced into a second loop reactor having a volume of 500 dm 3 operating at 95°C and 60 bar. Additional ethylene, propane and hydrogen were added so as to produce a polyethylene at 27 kg/hour having MFR 2 500 g/10 min and density 974 kg/m 3 .
- the polymer (still containing the active catalyst) was separated from the reaction medium and transferred to a gas phase reactor where additional hydrogen, ethylene and 1-butene comonomer were added so as to produce a polyethylene at 70 kg/hour having MFR 2 4 g/10 min and density 953 kg/m 3 .
- the fraction of high MFR (low MW) material in the total polymer was thus 40%. Three samples, denoted 3, 4 and 5, were produced in this manner.
- Table 2 clearly shows the bimodal HDPE to have superior ESCR properties.
- Samples 3 and 4 in particular had excellent warpage and shrinkage properties.
- Extrusion coating runs were made on a beloit pilot line using UG paper of 70 g/m 2 weight.
- the coating was a coextruded structure comprising a commercially available LDPE (LE 7518 from Borealis) and Sample 5 of Example 2 above at coating weights of 20 and 10 g/m 2 respectively.
- the structure was thus paper -LE 7518 - sample 5.
- Corona treatment was used to improve adhesion to paper.
- Different line speeds were tested between 100 and 500 m/min and line behaviour was acceptable even at the highest speed.
- a sample was taken and tested for water vapour transmission rate (WVTR) (measured at 90% relative humidity and 38°C according to ASTM - E96). WVTR was found to be 10.3 g/m 2 /24 hours.)
- WVTR water vapour transmission rate
- a coated structure was produced in the same way using a commercially available unimodal HDPE (HE 7012 from Borealis, R2 in Table 2 above) in place of Sample 5.
- the WVTR was found to be 11.8g/m 2 /24 hour, i.e. a higher value even though the density of R2 is greater than that of Sample 5.
- the bimodal HDPE thus has improved barrier properties relative to conventional materials.
Abstract
Description
- The invention relates to improvements in and relating to high density polyethylenes (HDPE) and in particular to the use of HDPE for injection moulding.
- HDPE is a polymer which is often used for the production by injection moulding of products used for packaging or containers. The HDPE materials conventionally used for these purposes are generally monomodal polyethylenes prepared using Ziegler-Natta catalysts.
- Where products are produced by injection moulding, it is important that the warpage in the product be low as otherwise the physical appearance of the product is poor.
- Moreover, where an injection moulded HDPE product is to be used to contain liquids where spillage would be environmentally undesirable, it is important that the moulded polymer is resistant to stress cracking. This may be measured by the environmental stress crack resistance (ESCR) test, a standardized ASTM test (e.g. ASTM D1693. Cond B).
- The standard commercially available HDPE injection moulding materials however have unsatisfactorily low ESCR values and thus are unsuitable for the production of injection moulded containers or other packaging materials for liquid chemical products, such as liquid chemicals, glues, paints, varnishes, solvent-based soaps etc.
- The polymers used for injection moulding are monomodal (ie. with a single peak in their molecular weight distributions). This is in order to avoid warpage.
- However, despite the conventional wisdom that it is essential to use monomodal HDPE for injection moulding, we have now surprisingly found that by using bimodal or multimodal HDPE wherein at least one of the polyethylene components is an ethylene copolymer, it is possible to produce injection moulded products with improved ESCR and warpage.
- Viewed from one aspect the invention thus provides the use in injection moulding, preferably in injection moulding of liquids containers, caps and closures, of a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- While the different components may both be ethylene copolymers and while one may be an ethylene homopolymer, the components cannot both be ethylene homopolymers. Where one of the components is an ethylene homopolymer, this is preferably the component with the lower weight average molecular weight (Mw), e.g. where Mw is 5000 to 100000 D, more preferably 20000 to 40000 D.
- Viewed from a further aspect the invention provides an injection moulded liquids container, preferably a container for liquids comprising an organic solvent, the walls whereof are formed from a HOPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- Viewed from a further aspect the invention provides an injection or extrusion moulded cap or closure, preferably a cap or closure for a container for beverages or liquids comprising an organic solvent, which cap or closure is formed from a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- Viewed from a further aspect the invention provides an HDPE for use in injection moulding, comprising at least two polyethylene components, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer.
- By polyethylene is meant a polymer the majority by weight of which derives from ethylene monomer units. Minor comonomer contributions, e.g. up to 20% by weight more preferably up to 10% by weight, may derive from other copolymerizable monomers, generally C3-20, especially C3-10, comonomers, particularly singly or multiply ethylenically unsaturated comonomers; in particular C3-10 α-olefins such as propene, but-1-ene, hex-1-ene, 4-methyl-pent-1-ene etc. It may be noted that the term ethylene copolymer is used herein to relate to a polyethylene deriving from ethylene and one or more such copolymerisable comonomers. Moreover, the polyethylene may contain minor, e.g up to 10% by weight, preferably up to 5% by weight of other polymers, e.g. other polyolefins in particular polypropylenes, as well as additives such as colours, fillers, radiation stabilizers, antioxidants, etc., generally in amounts of up to 10% by weight, preferably up to 5% by weight.
- By HOPE is meant a polyethylene having a density of 950 to 980 kg/m3, preferably 950 to 975 kg/m3, especially 950 to 965 kg/m3 and a crystallinity of 60 to 90%, preferably 70 to 90%.
- The HOPE according to the invention is a bimodal or multimodal polymer. By bimodal (or multimodal), it is meant that the polymer consists of at least two fractions (components), one of which has a relatively low molecular weight and a relatively high density and another of which has a relatively high molecular weight and a relatively low density. Typically the molecular weight distribution (MWD) of a polymer produced in a single polymerization stage using a single monomer mixture, a single polymerization catalyst and a single set of process conditions (ie. temperature, pressure etc.) will show a single maximum, the breadth of which will depend on catalyst choice, reactor choice, process conditions, etc, ie. such a polymer will be monomodal.
- A bimodal or multimodal polyethylene may be produced by blending two or more monomodal polyethylenes having differently centred maxima in their MWDs. Alternatively and preferably the bimodal polyethylene may be produced by polymerization using conditions which create a bimodal or multimodal polymer product, e.g. using a catalyst system or mixture with two or more different catalytic sites, using two or more stage polymerisation process with different process conditions in the different stages (e.g. different temperatures, pressures, polymerisation media, hydrogen partial pressures, etc).
- Such a bimodal (or multimodal) HOPE may be produced relatively simply by a multistage ethylene polymerization, e.g. using a series of reactors, with comonomer addition in only the reactor(s) used for production of the higher/highest molecular weight component(s). Examples of bimodal PE production are given in EP-A-778289 and WO92/12182.
- If an ethylene homopolymer component is produced by slurry polymerization involving use of recycled diluent, that diluent may contain small amounts of higher α-olefins as contaminants. Likewise where an earlier polymerization stage has produced an ethylene copolymer component, small amounts of comonomer may be carried over to an ethylene homopolymerization stage.
Accordingly, by ethylene homopolymer is meant herein a polymer containing at least 99.9% by weight of ethylene units. Likewise as in a multistage/multireactor polymerization using more than one catalyst system, the homopolymerization catalysts may be at least partially active during the copolymerization reaction, any copolymer component making up less than 5% by weight of the total polymer shall not be considered to be the lowest molecular weight component in an HDPE according to the invention. - The copolymer component(s) of the HDPE used according to the invention will generally contain at least 0.1% by weight, preferably at least 0.5% by weight of non-ethylene monomer units, e.g. 0.5 to 6% of such comonomer units.
- The polymerization reactions used to produce the HDPE of the invention may involve conventional ethylene homopolymerization or copolymerization reactions, e.g. gas-phase, slurry phase, liquid phase polymerizations, using conventional reactors, e.g. loop reactors, gas phase reactors, batch reactors etc. (see for example WO97/44371 and WO96/18662). The catalyst systems used may likewise be any conventional systems, e.g. chromium catalysts, Ziegler-Natta and metallocene or metallocene:aluminoxane catalysts, either homogeneous or more preferably heterogeneous catalysts, e.g. catalysts supported on inorganic or organic particulates, in particular on magnesium halides or inorganic oxides such as silica, alumina or silica-alumina. For the preparation of the high molecular weight component in particular it is especially desirable to use supported Ziegler-Natta catalysts as the molecular weight can then conveniently be controlled using hydrogen. It is also possible to use supported metallocene catalysts as it is particularly straightforward to select desired molecular weights by appropriate selection of particular metallocenes. The metallocenes used will typically be group IVa to VIa metals (in particular Zr or Hf) complexed by optionally substituted cyclopentadienyl groups, e.g. groups carrying pendant or fused substituents optionally linked together by bridging groups. Suitable metallocenes and aluminoxane cocatalysts are widely described in the literature, e.g. the patent publications of Borealis, Hoechst, Exxon, etc.
- Typically and preferably however the HOPE will be prepared using multistage polymerization using a single catalyst system or a plurality of catalyst systems, e.g. two or more metallocenes, one or more metallocenes and one or more Ziegler-Natta catalysts, two or more chromium catalysts, one or more chromium catalysts and one or more Ziegler-Natta catalysts, etc. Especially preferably the same catalyst system is used in the different polymerization stages, e.g. a catalyst system as described in EP-A-688794.
- The properties of the HDPE used according to the invention preferably have the following values:
- MFR2 of 50-1000 g/10 min, preferably 200-800 g/10 min, measured according to ISO 1133 at 190°C and under 2.16 kg load;
weight average molecular weight of 5-50 kD, preferably 20-40 kD;
preferably a homopolymer or a copolymer with density higher than 965 kg/m3, most preferably a homopolymer;
comprises 10-90% by weight, preferably 40-60% by weight of the total polyethylene in the composition. - Has molecular weight and comonomer content such that the final polymer composition has the desired preset MFR and density;
weight average molecular weight of 150-400 kD;
comprises 10-90% by weight, preferably 40-60% by weight of the total polyethylene in the composition, i.e. low mw:high mw component weight ratio is 10:90 to 90:10, preferably 40:60 to 60:40. - MFR2 of 2-100 g/10 min, preferably 3-50 g/10 min, in particular 4-20 g/10 min, measured according to ISO 1133 at 190° and under 2.16 kg load;
weight average molecular weight of 80-200, preferably 100-180 kD;
molecular weight distribution (ratio of the weight average molecular weight to the number average molecular weight) of 5-100, preferably 10-60, more preferably 14-45;
density of 940-980 kg/m3, preferably 945-975 kg/m3, in particular 950-965 kg/m3;
comonomer content of 0.2-10% by weight, preferably 1-3% by weight, as measured by FTIR;
crystalline melting point between 120 and 140°C, as determined by DSC analysis;
crystallinity of 60-90%, as determined by DSC analysis. - ESCR F50 higher than 10 h, preferably higher than 40 h, measured according to ASTM D1693, Condition B;
improvement in ESCR, measured as above, relative to a standard unimodal material HE7004 (manufactured and sold by Borealis) of 50-1000%, preferably of 500-1000%;
E-modulus of at least 800 MPa (measured according to ISO 527-2);
Impact strength of 30-200 kJ/m2 (measured according to ISO 8256-A). - Such HDPE may typically be prepared in a one or more stage polymerization, with the catalyst systems and process conditions in the individual stages being selected to produce polyethylene components of average molecular weights 5 to 100 kD and 150 to 400 kD in abundances of 1:9 to 9:1.
- For injection moulding of the resultant HDPE, conventional moulding equipment may be used, e.g. operating at an injection temperature of 190 to 275°C, Typically containers produced in this fashion will have a volume of 100 mL to 100 L and caps and closures will typically have maximum dimensions of 10 to 600 mm.
- The injection moulding compositions of the invention have the further advantage of improved flow. This may be demonstrated using the 'spiral test'. In this procedure an Engel ES330/65 injection moulding apparatus is used with a spiral mould with a depth of 1, 2 or typically 3 mm. The composition flow rate at 230°C under 300, 500 and 700 bar follow up pressures is determined on the length of flow in the spiral. Typically a composition according to the invention with an MFR2 value of about 4 g/10 min behaves like a conventional polyethylene with MFR2 of about 8 g/10 min. See Table 1 below.
Modality MFR2(g/10 min) Flow (cm) at pressure (p) (bar) p=300 p=500 p=700 Bimodal 4 32.6 47.5 61.3 Unimodal 2 21.5 32.3 41.6 Unimodal 4 27.1 39.8 52.5 Unimodal 8 35.2 50.2 65.2 Unimodal 12 40.8 57.2 72.5 - Besides being useful for injection moulding, it has also been found that the bimodal and multimodal HDPEs used according to the invention are particularly useful for extrusion coating, e.g. of paper or other substrates, producing coatings with low water vapor permeability and good coating draw down rates. Such use of the bimodal and multimodal HDPE's (especially ones with densities in excess of 935 kg/m3) forms a further aspect of the invention.
- Viewed from a still further aspect the invention provides an HDPE comprising at least two polyethylene components, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer and having the following characteristics:
- MFR2 of from 2 to 100;
- mean weight average molecular weight of from 80 to 200 kD;
- MWD of from 5 to 100;
- weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;
- weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;
- weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;
- melting point 120 to 140°C;
- density 950 to 980 kg/m3;
- comonomer content 0.2 to 10% by weight; and
- crystallinity 60 to 90%.
-
- Viewed from a yet further aspect the invention provides an HDPE moulding composition comprising a particulate HOPE having the following characteristics:
- MFR2 of from 2 to 100;
- mean weight average molecular weight of from 80 to 200 kD;
- MWD of from 5 to 100;
- weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;
- weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;
- weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;
- melting point 120 to 140°C;
- density 950 to 980 kg/m3;
- comonomer content 0.2 to 10% by weight; and
- crystallinity 60 to 90% together with at least one additive or further polymer.
-
- Viewed from another aspect the invention provides an injection moulded article formed at least in part from an HDPE having the following characteristics:
- MFR2 of from 2 to 100;
- mean weight average molecular weight of from 80 to 200 kD;
- MWD of from 5 to 100;
- weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;
- weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;
- weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;
- melting point 120 to 140°C;
- density 950 to 980 kg/m3;
- comonomer content 0.2 to 10% by weight; and crystallinity 60 to 90%.
-
- The invention will now be described further by reference to the following non-limiting Examples:
- Two bimodal polyethylene compositions (Samples 1 and 2) were prepared by mixing two of the three polyethylene components (A, B and C) listed in Table 1 into blends using an extruder (Werner & Pfleider ZSK 30W) operating at 193-194°C.
Component Property Component A B C Mw(kD) 190 400 28 Mn (kD) 6 56 2.5 MWD 32 7 11 MFR21 (g/10 min) 33 0.1 400 Density (kg/m3) 955 927 974 - Sample 1 comprised 40% wt component C and 60% wt component A. Sample 2 comprised 60% wt component C and 40 wt% component B.
- The properties of the blends are shown in Table 2 below.
- Into a 50 dm3 loop reactor, operated at 80°C and 65 bar, was introdcued 1 kg/hour ethylene, 22 kg/hour propane, 2g/hour hydrogen and the polymerization catalyst of Example 3 of EP-B-688794 (loaded on 20 micron silica) in a quantity such that PE production rate was 6.8 kg PE/hour. The MFR2 and density of the product are estimated at 30 g/10 min and 970 kg/m3 respectively.
- The slurry was continuously removed from the loop reactor and introduced into a second loop reactor having a volume of 500 dm3 operating at 95°C and 60 bar. Additional ethylene, propane and hydrogen were added so as to produce a polyethylene at 27 kg/hour having MFR2 500 g/10 min and density 974 kg/m3. The polymer (still containing the active catalyst) was separated from the reaction medium and transferred to a gas phase reactor where additional hydrogen, ethylene and 1-butene comonomer were added so as to produce a polyethylene at 70 kg/hour having MFR2 4 g/10 min and density 953 kg/m3. The fraction of high MFR (low MW) material in the total polymer was thus 40%. Three samples, denoted 3, 4 and 5, were produced in this manner.
- The properties of samples 1 to 5 are set out in Table 2 below.
- A commercially available unimodal reference material HE 7004 (Borealis) was similarly evaluated. The results are designated R1.
Samples: 1 2 3 4 5 R1 R2 Mw Weight Average 121 170 102 106 105 105 70 Molecular Weight (kD) Mn Number Average 4.2 4.1 7 7.4 7.2 16 13 Molecular Weight (kD) MWD 29 41 14.5 14.3 14.2 6 5.5 MFR2 g/10 min 2.6 1.7 3.9 3.2 4.8 4.0 12 Density (kg/m3) 963 956 953 953 957 954 964 Ratio LMW/HMW 40/60 60/40 40/60 40/60 40/60 ESCR, F50 (hours) 46 86 46 43 9 ESCR improvement (%) 411 856 411 378 0 E-modulus (kPa) 1080 930 880 830 850 Comonomer content 0.5 1.1 1.4 1.4 <0.1 (wt %) - Table 2 clearly shows the bimodal HDPE to have superior ESCR properties.
- Samples 3 and 4 in particular had excellent warpage and shrinkage properties.
- Using Samples 1 and 2 of Example 1, pails were produced by injection moulding. Specimens were cut from the walls of the pails and placed in a liquid containing 25 or 40% turpentine. Both samples produced products which showed approvable swell behaviour and stiffness in this test.
- Extrusion coating runs were made on a beloit pilot line using UG paper of 70 g/m2 weight. The coating was a coextruded structure comprising a commercially available LDPE (LE 7518 from Borealis) and Sample 5 of Example 2 above at coating weights of 20 and 10 g/m2 respectively. The structure was thus paper -LE 7518 - sample 5. Corona treatment was used to improve adhesion to paper. Different line speeds were tested between 100 and 500 m/min and line behaviour was acceptable even at the highest speed. A sample was taken and tested for water vapour transmission rate (WVTR) (measured at 90% relative humidity and 38°C according to ASTM - E96). WVTR was found to be 10.3 g/m2/24 hours.)
- By way of comparison, a coated structure was produced in the same way using a commercially available unimodal HDPE (HE 7012 from Borealis, R2 in Table 2 above) in place of Sample 5. The WVTR was found to be 11.8g/m2/24 hour, i.e. a higher value even though the density of R2 is greater than that of Sample 5.
- The bimodal HDPE thus has improved barrier properties relative to conventional materials.
Claims (15)
- The use in injection moulding or extrusion coating of a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- Use as claimed in claim 1 of a said HDPE for injection moulding of liquids containers, closures or caps.
- Use as claimed in either of claims 1 or 2 of an HDPE having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90;10; melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
- Use as claimed in any one of claims 1 to 3 wherein said HDPE has a weight ratio of low molecular weight fraction to high molecular weight fraction of 40:60 to 60:40.
- An injection moulded liquids container the walls whereof are formed from a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- A container as claimed in claim 5 formed from a said HDPE having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10; melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
- An injection or extrusion moulded cap or closure, which cap or closure is formed from a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- A cap or closure as claimed in claim 7 formed from a said HDPE having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
- An extrusion coated structure having at least one extruded layer formed from a HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% comprising at least two polyethylene components having different molecular weight distributions wherein at least one of said components is an ethylene copolymer.
- A structure as claimed in claim 9 wherein said at least one extruded layer is formed from a HDPE having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
- A structure as claimed in claim 9 or claim 10 wherein said HDPE has a density of 955-975 kg/m3.
- An HDPE having a density of 950 to 980 kg/m3 and a crystallinity of 60 to 90% for use in injection moulding or extrusion coating, comprising at least two polyethylene components having different molecular weight distributions, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer synthesised using a Ziegler-Natta or metallocene catalyst.
- An HDPE comprising at least two polyethylene components, wherein at least one said component is an ethylene copolymer and wherein at least the component with the lowest weight average molecular weight is an ethylene homopolymer, and having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
- An HDPE moulding composition comprising a particulate HDPE as defined in claim 13 together with at least one additive or further polymer.
- An injection moulded article formed at least in part from an HDPE having the following characteristics:MFR2 of from 2 to 100;mean weight average molecular weight of from 80 to 200 kD;MWD of from 5 to 100;weight average molecular weight of a low molecular weight fraction of 20 to 40 kD;weight average molecular weight of a high molecular weight fraction of 150 to 400 kD;weight ratio of said low molecular weight fraction to said high molecular weight fraction of 10:90 to 90:10;melting point 120 to 140°C;density 950 to 980 kg/m3;comonomer content 0.2 to 10% by weight; andcrystallinity 60 to 90%.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9911934.9A GB9911934D0 (en) | 1999-05-21 | 1999-05-21 | Polymer |
GB9911934 | 1999-05-21 | ||
PCT/GB2000/001959 WO2000071615A1 (en) | 1999-05-21 | 2000-05-22 | Injection moulding |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1187876A1 EP1187876A1 (en) | 2002-03-20 |
EP1187876B1 true EP1187876B1 (en) | 2003-04-23 |
Family
ID=10853964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00935303A Revoked EP1187876B1 (en) | 1999-05-21 | 2000-05-22 | Injection moulding |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1187876B1 (en) |
CN (1) | CN1122686C (en) |
AT (1) | ATE238387T1 (en) |
AU (1) | AU5085700A (en) |
DE (1) | DE60002322T2 (en) |
ES (1) | ES2198314T3 (en) |
GB (1) | GB9911934D0 (en) |
WO (1) | WO2000071615A1 (en) |
Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1310436A1 (en) | 2001-11-09 | 2003-05-14 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Screw cap comprising a multimodal polyethylene composition |
US7196138B2 (en) * | 2001-12-14 | 2007-03-27 | Corrugatedd Polyethylene Pipe Ltd. | Melt blended high density polyethylene compositions with enhanced properties and method for producing the same |
US7317054B2 (en) | 2001-12-14 | 2008-01-08 | Corrugated Polyethleyne Pipe, Ltd. | Melt blended high density polyethylene compositions with enhanced properties and method for producing the same |
DE60202660T3 (en) † | 2002-02-04 | 2011-11-17 | Borealis Technology Oy | Film with high impact resistance |
EP1384751A1 (en) * | 2002-07-25 | 2004-01-28 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Container formed from multimodal ethylene polymer |
BE1015053A3 (en) * | 2002-07-25 | 2004-09-07 | Solvay | A composition used for screw caps for bottles, especially aerated drink bottles, based on a multimodal ethylene polymer comprising an ethylene polymer and an ethylene-3-12C olefin copolymer with specified densities and fluidity index |
US7396878B2 (en) | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for injection molding |
US7396881B2 (en) | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for rotational molding |
WO2004031293A1 (en) | 2002-10-01 | 2004-04-15 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for rotational molding |
EP1449878A1 (en) * | 2003-02-24 | 2004-08-25 | Borealis Technology Oy | Polypropylene compositions |
US20050142312A1 (en) * | 2003-12-29 | 2005-06-30 | Unilever Home & Personal Care Usa | Bottle |
EP1555292B1 (en) * | 2004-01-13 | 2015-12-23 | Borealis Technology Oy | Extrusion coating polyethylene |
DE102004020524A1 (en) | 2004-04-26 | 2005-11-10 | Basell Polyolefine Gmbh | Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes |
GB0419852D0 (en) * | 2004-09-07 | 2004-10-13 | Borealis Tech Oy | Injection moulded article |
DE602004004405T3 (en) † | 2004-11-03 | 2012-12-20 | Borealis Technology Oy | Multimodal polyethylene composition for injection-molded transport packaging |
ES2277186T3 (en) | 2004-11-03 | 2007-07-01 | Borealis Technology Oy | COMPOSITION OF MULTIMODAL POLYETHYLENE FOR COVERS MOLDED BY INJECTION AND CLOSURE DEVICES. |
EP1674523A1 (en) * | 2004-12-22 | 2006-06-28 | Total Petrochemicals Research Feluy | Caps and closures |
CN101087824B (en) | 2005-01-12 | 2011-02-16 | 波利亚里斯技术有限公司 | Extrusion coating polyethylene |
DE102005019393A1 (en) | 2005-04-25 | 2006-10-26 | Basell Polyolefine Gmbh | Molding material, useful for the preparation of injection-molded body and screw valve, comprises ethylene monomer |
DE602005016257D1 (en) | 2005-09-22 | 2009-10-08 | Borealis Tech Oy | Polyethylene composition with a broad molecular weight distribution |
US7595364B2 (en) | 2005-12-07 | 2009-09-29 | Univation Technologies, Llc | High density polyethylene |
EP1834986A1 (en) * | 2006-03-13 | 2007-09-19 | Borealis Technology Oy | High density polyethylene |
ATE535569T1 (en) | 2006-12-29 | 2011-12-15 | Borealis Tech Oy | POLYETHYLENE COMPOUNDS FOR BLOW-MOLDED TRANSPORT PACKAGING ARTICLES |
WO2008092736A1 (en) | 2007-02-01 | 2008-08-07 | Basell Polyolefine Gmbh | Monomodal copolymer of ethylene for injection molding and process for its preparation |
DE602007003611D1 (en) | 2007-05-02 | 2010-01-14 | Dow Global Technologies Inc | HIGH-DENSITY POLYETHYLENE COMPOSITIONS, METHOD FOR THE PRODUCTION THEREOF, INJECTION-MOLDED ARTICLES MADE THEREFROM AND METHOD FOR THE PRODUCTION OF SUCH ITEMS |
EP2011822A1 (en) * | 2007-07-04 | 2009-01-07 | Borealis Technology Oy | Multimodal polyethylene co-polymer resin composition, a preparation process therefore and a polymeric product comprising the same |
ATE491647T1 (en) | 2007-08-10 | 2011-01-15 | Borealis Tech Oy | ITEM CONTAINING A POLYPROPYLENE COMPOSITION |
EP2067799A1 (en) | 2007-12-05 | 2009-06-10 | Borealis Technology OY | Polymer |
CA2711048C (en) | 2007-12-31 | 2018-02-27 | Dow Global Technologies Inc. | Ethylene-based polymer compositions, methods of making the same, and articles prepared from the same |
CA2629576C (en) | 2008-04-21 | 2016-01-05 | Nova Chemicals Corporation | Closures for bottles |
WO2010022941A1 (en) | 2008-08-29 | 2010-03-04 | Basell Polyolefine Gmbh | Polyethylene for injection moldings |
DK2451851T3 (en) * | 2009-07-10 | 2016-01-04 | Total Res & Technology Feluy | Caps and lids |
EP2354183B1 (en) | 2010-01-29 | 2012-08-22 | Borealis AG | Moulding composition |
EP2354184B1 (en) | 2010-01-29 | 2012-08-22 | Borealis AG | Polyethylene moulding composition with improved stress crack/stiffness relationship and impact resistance |
EP2402391B1 (en) * | 2010-06-29 | 2013-07-31 | Borealis AG | Bimodal polyethylene composition for injection moulded articles |
CN103347950B (en) * | 2011-01-28 | 2016-05-25 | 博里利斯股份公司 | Polyethylene composition |
US9371442B2 (en) | 2011-09-19 | 2016-06-21 | Nova Chemicals (International) S.A. | Polyethylene compositions and closures made from them |
CA2752407C (en) | 2011-09-19 | 2018-12-04 | Nova Chemicals Corporation | Polyethylene compositions and closures for bottles |
WO2013045663A1 (en) * | 2011-09-30 | 2013-04-04 | Total Research & Technology Feluy | High-density polyethylene for caps and closures |
GB2498936A (en) | 2012-01-31 | 2013-08-07 | Norner Innovation As | Polyethylene with multi-modal molecular weight distribution |
US9475927B2 (en) | 2012-12-14 | 2016-10-25 | Nova Chemicals (International) S.A. | Polyethylene compositions having high dimensional stability and excellent processability for caps and closures |
US9783663B2 (en) | 2012-12-14 | 2017-10-10 | Nova Chemicals (International) S.A. | Polyethylene compositions having high dimensional stability and excellent processability for caps and closures |
CN104558747B (en) * | 2013-10-23 | 2017-01-18 | 中国石油化工股份有限公司 | Quickly molded high density polyethylene composition and preparation method thereof |
EP2891680B1 (en) * | 2014-01-06 | 2017-03-08 | Borealis AG | Polymer blend: HDPE with ethylene-norbornene or propylene-norbornene copolymer |
CN105294888B (en) * | 2014-06-06 | 2019-03-29 | 中国石油化工股份有限公司 | High-crystallinity broad peak polyvinyl resin and preparation method thereof |
ES2713632T3 (en) * | 2014-12-30 | 2019-05-23 | Abu Dhabi Polymers Co Ltd Borouge Llc | HDPE |
CN107922681A (en) | 2015-06-30 | 2018-04-17 | 陶氏环球技术有限责任公司 | Vinyl polymer compositions for improved extrusion coating |
US9758653B2 (en) | 2015-08-19 | 2017-09-12 | Nova Chemicals (International) S.A. | Polyethylene compositions, process and closures |
KR101692346B1 (en) * | 2016-04-27 | 2017-01-03 | 한화케미칼 주식회사 | High density ethylene polymer using supported hybrid metallocene catalyst and methods for producing the same |
CA2931488A1 (en) | 2016-05-30 | 2017-11-30 | Nova Chemicals Corporation | Closure having excellent organoleptic performance |
US9783664B1 (en) | 2016-06-01 | 2017-10-10 | Nova Chemicals (International) S.A. | Hinged component comprising polyethylene composition |
AR109705A1 (en) * | 2016-09-30 | 2019-01-16 | Dow Global Technologies Llc | HIGH PROCESSABILITY POLYETHYLENE COMPOSITIONS FOR INJECTION MOLDED ITEMS |
EP3559092B9 (en) | 2016-12-22 | 2022-07-20 | Dow Global Technologies LLC | Process to make high density ethylene-based polymer compositions with high melt strength |
EP3749707A1 (en) | 2018-02-05 | 2020-12-16 | ExxonMobil Chemical Patents Inc. | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
CA3028148A1 (en) | 2018-12-20 | 2020-06-20 | Nova Chemicals Corporation | Polyethylene copolymer compositions and articles with barrier properties |
EP4003684A1 (en) | 2019-07-25 | 2022-06-01 | Nova Chemicals (International) S.A. | Rotomolded parts prepared from bimodal polyethylene |
CA3203104A1 (en) | 2020-12-22 | 2022-06-30 | Ineos Europe Ag | Polymer composition for caps and closures |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451873A (en) * | 1980-03-10 | 1984-05-29 | General Motors Corporation | Reflector for a sealed beam lamp |
JPH03115445A (en) * | 1989-09-29 | 1991-05-16 | Nippon Petrochem Co Ltd | Ethylenic polymer composition |
KR930006091A (en) * | 1991-09-18 | 1993-04-20 | 제이 이이 휘립프스 | Polyethylene blends and films, bottles or pipes made therefrom |
FI98819C (en) * | 1993-03-26 | 1997-08-25 | Borealis Polymers Oy | Process for the production of olefin polymers and products made with the process |
US5811494A (en) * | 1995-04-06 | 1998-09-22 | The Dow Chemical Company | Impact modified thinwall polymer compositions |
-
1999
- 1999-05-21 GB GBGB9911934.9A patent/GB9911934D0/en not_active Ceased
-
2000
- 2000-05-22 WO PCT/GB2000/001959 patent/WO2000071615A1/en active Application Filing
- 2000-05-22 AU AU50857/00A patent/AU5085700A/en not_active Abandoned
- 2000-05-22 EP EP00935303A patent/EP1187876B1/en not_active Revoked
- 2000-05-22 CN CN00809774.7A patent/CN1122686C/en not_active Expired - Fee Related
- 2000-05-22 ES ES00935303T patent/ES2198314T3/en not_active Expired - Lifetime
- 2000-05-22 DE DE60002322T patent/DE60002322T2/en not_active Revoked
- 2000-05-22 AT AT00935303T patent/ATE238387T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE60002322D1 (en) | 2003-05-28 |
DE60002322T2 (en) | 2004-04-08 |
WO2000071615A1 (en) | 2000-11-30 |
AU5085700A (en) | 2000-12-12 |
EP1187876A1 (en) | 2002-03-20 |
GB9911934D0 (en) | 1999-07-21 |
CN1359409A (en) | 2002-07-17 |
ATE238387T1 (en) | 2003-05-15 |
ES2198314T3 (en) | 2004-02-01 |
CN1122686C (en) | 2003-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1187876B1 (en) | Injection moulding | |
EP2010603B1 (en) | Polyolefin compositions, articles made therefrom and methods for preparing the same | |
KR101768245B1 (en) | Moulding composition | |
US7378472B2 (en) | Injection moulding polymer | |
AU2001264132B2 (en) | Injection moulding polymer | |
US7569175B1 (en) | Container production process | |
KR910008600B1 (en) | Poly olefin composition | |
AU2001264132A1 (en) | Injection moulding polymer | |
EP1730230B1 (en) | Polyethylene blends with good contact transparency | |
EP1593696A2 (en) | Metallocene-produced polyethylene for glossy plastic containers | |
US20100227098A1 (en) | Ethylenic Resin and Blow Molded Article Obtained Therefrom | |
EP3880749A1 (en) | Composition | |
JP2004168817A (en) | Polyethylene composition | |
JP6331899B2 (en) | Ethylene polymer composition for thin-walled container and molded body comprising the same | |
JP2004059650A (en) | Polyethylene composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20011113 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030423 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030423 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030522 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030522 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030522 |
|
REF | Corresponds to: |
Ref document number: 60002322 Country of ref document: DE Date of ref document: 20030528 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030723 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030723 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: A. BRAUN, BRAUN, HERITIER, ESCHMANN AG PATENTANWAE |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20030423 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2198314 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
26 | Opposition filed |
Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20040123 Opponent name: SOLVAY POLYOLEFINS EUROPE-BELGIUM (SOCIETE ANONYME Effective date: 20040121 Opponent name: BASELL POLYOLEFINE GMBH Effective date: 20030123 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Opponent name: BASELL POLYOLEFINE GMBH Opponent name: SOLVAY POLYOLEFINS EUROPE-BELGIUM (SOCIETE ANONYME |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: BASELL POLYOLEFINE GMBH Effective date: 20030123 Opponent name: INNOVENE MANUFACTURING BELGIUM N.V Effective date: 20040121 Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20040123 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Opponent name: INNOVENE MANUFACTURING BELGIUM N.V Opponent name: BASELL POLYOLEFINE GMBH |
|
R26 | Opposition filed (corrected) |
Opponent name: BASELL POLYOLEFINE GMBH Effective date: 20030123 Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20040123 Opponent name: INNOVENE MANUFACTURING BELGIUM N.V Effective date: 20040121 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: INNOVENE MANUFACTURING BELGIUM N.V Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Opponent name: BASELL POLYOLEFINE GMBH |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: INEOS MANUFACTURING BELGIUM NV Effective date: 20040121 Opponent name: BASELL POLYOLEFINE GMBH Effective date: 20030123 Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20040123 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: BASELL POLYOLEFINE GMBH Opponent name: INEOS MANUFACTURING BELGIUM NV Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: BASELL POLYOLEFINE GMBH Effective date: 20030123 Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20040123 Opponent name: INEOS MANUFACTURING BELGIUM NV Effective date: 20040121 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: EXXONMOBIL CHEMICAL PATENTS INC. Opponent name: BASELL POLYOLEFINE GMBH Opponent name: INEOS MANUFACTURING BELGIUM NV |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: BOREALIS TECHNOLOGY OY Free format text: BOREALIS TECHNOLOGY OY#P.O.BOX 330#06101 PORVOO (FI) -TRANSFER TO- BOREALIS TECHNOLOGY OY#P.O.BOX 330#06101 PORVOO (FI) |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20100525 Year of fee payment: 11 Ref country code: FI Payment date: 20100514 Year of fee payment: 11 Ref country code: FR Payment date: 20100611 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20100514 Year of fee payment: 11 Ref country code: IT Payment date: 20100522 Year of fee payment: 11 Ref country code: DE Payment date: 20100521 Year of fee payment: 11 Ref country code: AT Payment date: 20100513 Year of fee payment: 11 |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20100525 Year of fee payment: 11 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20100517 Year of fee payment: 11 Ref country code: GB Payment date: 20100519 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
27W | Patent revoked |
Effective date: 20100825 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Effective date: 20100825 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: ECNC |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20030423 Ref country code: LI Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20030423 |